CN105086996B - A kind of tripolyphosphazene crosslinking rare-earth complexes luminous material and preparation method thereof - Google Patents
A kind of tripolyphosphazene crosslinking rare-earth complexes luminous material and preparation method thereof Download PDFInfo
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- CN105086996B CN105086996B CN201510529584.6A CN201510529584A CN105086996B CN 105086996 B CN105086996 B CN 105086996B CN 201510529584 A CN201510529584 A CN 201510529584A CN 105086996 B CN105086996 B CN 105086996B
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- YJMHWSGZMMMCPL-UHFFFAOYSA-N CC1C=CC(N)=CC1C Chemical compound CC1C=CC(N)=CC1C YJMHWSGZMMMCPL-UHFFFAOYSA-N 0.000 description 1
- RGHPCLZJAFCTIK-RXMQYKEDSA-N C[C@H]1NCCC1 Chemical compound C[C@H]1NCCC1 RGHPCLZJAFCTIK-RXMQYKEDSA-N 0.000 description 1
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Abstract
The present invention relates to a kind of tripolyphosphazene crosslinking rare-earth complexes luminous material and preparation method thereof, the general structure of tripolyphosphazene crosslinking rare earth compounding is as follows：
Description
Technical field
The present invention relates to rare earth luminescent material field, and in particular to a kind of tripolyphosphazene is crosslinked rare-earth complexes luminous material
And preparation method thereof.
Background technology
Rare earth is new function material that is a kind of while having the multifrequency natures such as light, magnetic, electricity and biology.Rare earth ion because
Possess the luminosity of uniqueness for the unique texture of its 4f electronic shell.Rare earth compounding is bonded by ligand with rare-earth ion coordination
And obtain, its principle of luminosity is that ligand absorbs energy in ultra-violet (UV) band, and then ligand is swashed in a manner of intramolecular charge-transfer transition
The energy transmission of hair state causes rare earth luminescence to the emission level of rare earth ion.
Rare earth luminescent material compared with other luminescent materials with excitation purity is high, luminous quantum efficiency is high, fluorescence lifetime is long,
The features such as fast response time.So rare earth is widely used in the research of field of light emitting materials.Its application range is related to electronics
The fields such as kinescope, fluorescence probe, laser, medical apparatus and instruments, light storage.But at present for rare earth compounding luminous intensity
The bottleneck that weak the solution method that has not found always of problem.
The content of the invention
In view of the above-mentioned problems existing in the prior art, it is an object of the present invention to provide a kind of good luminescence property
Tripolyphosphazene is crosslinked rare-earth complexes luminous material.
It is another object of the present invention to provide a kind of method is simple, the easy-operating tripolyphosphazene crosslinking rare earth for preparing is matched somebody with somebody
The method of compound luminescent material.
To realize above-mentioned first purpose, the present invention adopts the following technical scheme that：A kind of tripolyphosphazene crosslinking rare earth coordinates
Thing luminescent material, the general structure of tripolyphosphazene crosslinking rare earth compounding are as follows：
Wherein Ln is Eu or Tb.
To realize above-mentioned second purpose, the present invention adopts the following technical scheme that：Above-mentioned tripolyphosphazene crosslinking rare earth coordinates
The preparation method of thing luminescent material, includes the following steps：
S1：Six（4- potassium formate phenoxyls）The preparation of ring tripolyphosphazene：It is 1 in molar ratio:1~10:5 ~ 20 ratio takes
Hexa chloro cyclotripolyphosphazene, P-hydroxybenzoic acid and potassium carbonate mixing, add in good solvent and stir, dissolve solid, by reaction temperature
Degree is warming up to 40~90 DEG C, when sustained response 36~48 is small；
S2：Six（4- potassium formate phenoxyls）The purification of ring tripolyphosphazene：Step S1 products therefroms are cooled to room temperature, are used
Distilling apparatus distilling off solvent, then with DMF lysates, stirs 12h, filtering, obtains clear filtrate, rotate 3/4 filtrate
Afterwards, finally with ethyl acetate reprecipitation product, then with ethyl acetate washed product for several times, when vacuum drying 12~24 is small；
S3：Tripolyphosphazene is crosslinked the preparation of rare earth compounding：It is 1 in molar ratio:1 ~ 10 ratio takes TbCl3.6H2O and six
（4- potassium formate phenoxyls）Ring tripolyphosphazene, is then dissolved in solvent and fully dissolving respectively, then by TbCl3.6H2O solution and
Six（4- potassium formate phenoxyls）Ring tripolyphosphazene solution mixes, and is reacted, and reaction temperature is 40~90 DEG C, response duration
Between be 4~8h；
S4：Tripolyphosphazene is crosslinked the purification of rare earth compounding：After the completion of step S3 reactions, it is miscellaneous that grease is filtered out while hot
Matter, then rotates the solvent in reaction, then with absolute ethyl alcohol washing reaction products several times, finally sinks again in ethyl acetate
Form sediment product.
Under ultraviolet wavelength excitation, tripolyphosphazene terbium coordination compound launches pure green light, the transmitting of tripolyphosphazene europium complex
Go out pure feux rouges.
Preferably, the good solvent in the step S1 is dichloromethane, chloroform, tetrahydrofuran, N, N- dimethyl
One or more in formamide or dimethyl sulfoxide (DMSO).
Preferably, the hexa chloro cyclotripolyphosphazene is NH4Cl and PCl5React and be made in chlorobenzene solution.This method profit
By the use of chlorobenzene as reaction dissolvent, 132 DEG C of the boiling point of chlorobenzene is primarily due to, is adapted to reaction to require, reaction efficiency is high, if selecting it
His solvent, boiling point is excessive, easy generation linear polymer in reaction process, the too low other cyclic polymerizations of easy generation of boiling point
Thing, influences reaction yield.And select zinc oxide/pyridine to be used as acid binding agent as composite catalyst, wherein pyridine, absorb
The HCl generated in reaction, improves reaction efficiency.
Relative to the prior art, the invention has the advantages that：
1st, produced by the present invention is multi-kernel rare-earth complex rare earth luminescent material, and it is high to find excitation purity height, luminous efficiency
Screen is with the emphasis that rare earth material is that people study, but most of current trichromatic rare-earth complex is all monokaryon, double-core,
So the present invention has certain innovation and practicality.
2nd, six caryogamy bodies six prepared by the present invention（4- potassium formate phenoxyls）Ring tripolyphosphazene have can with europium from
Son and the ability of terbium ion coordination, and can effectively transfer energy to terbium ion or europium ion, thus launch europium from
The characteristic emission light of son and terbium ion.
3rd, the present invention utilizes strongly active and nitrogen phosphorus key the stiff stability synthesis trimerization phosphorus of chlorine phosphorus key in chlordene tripolyphosphazene
Nitrile is crosslinked rare earth compounding, since prepared rare earth compounding is crosslink type, molecule will not generation concentration be quenched, it is and single
In a molecule, the centre of luminescence is more, so the good luminescence property of complex.For monokaryon rare earth compounding, the ligand
It can be coordinated at the same time with six rare earth ions, obtained complex has high excellent luminescent properties.It is this kind of multi-functional
The exploitation of ligand, by the further application field for expanding rare earth luminescent material.
4th, tripolyphosphazene provided by the invention crosslinking rare-earth complexes luminous material is mainly used for computer, TV, mobile phone
Deng electric terminal, the luminescent material as flat display field.Other year-on-year luminescent materials, this material emission excellent performance can
As luminescence generated by light or the potential material in electroluminescent field.
5th, the preparation method of tripolyphosphazene crosslinking rare-earth complexes luminous material provided by the invention is simple, operability
By force, the reaction time is short, and environmentally protective, is adapted to industrial production.
Brief description of the drawings
Fig. 1 is that the tripolyphosphazene of the gained of embodiment 1 is crosslinked the infrared spectrogram (pressing potassium bromide troche) of rare-earth terbium complex.
Fig. 2 is that the tripolyphosphazene of the gained of embodiment 1 is crosslinked the fluorescent exciting spectrogram (transmitted wave of rare-earth terbium complex
It is long：545nm, slit 5nm, solid state powder).
Fig. 3 is that the tripolyphosphazene of the gained of embodiment 1 is crosslinked the fluorescence emission spectrogram of compound (excitation wave of rare-earth terbium complex
It is long：316nm, slit 5nm, solid state powder).
Fig. 4 is that the tripolyphosphazene of the gained of embodiment 2 is crosslinked the infrared spectrogram (pressing potassium bromide troche) of rare-earth terbium complex.
Fig. 5 is that the tripolyphosphazene of the gained of embodiment 2 is crosslinked the fluorescence emission spectrogram of compound (excitation wave of rare-earth terbium complex
It is long：291nm, slit 5nm, solid state powder).
Embodiment
The present invention is described in further detail below.For convenience of narration, tripolyphosphazene crosslinking rare earth is matched somebody with somebody in specification
Compound luminescent material is referred to as complex or tripolyphosphazene crosslinking rare earth compounding, by six（4- potassium formate phenoxyls）Ring trimerization
Phosphonitrile is referred to as ligand.
Embodiment 1：Tripolyphosphazene is crosslinked the preparation method of rare-earth complexes luminous material：
S1：Tetrahydrofuran 100ml hexa chloro cyclotripolyphosphazenes 2.50g is sequentially added in 250ml single-necked flasks
（7.19mmol）, P-hydroxybenzoic acid 7.13g（51.59mmol）, potassium carbonate 11.38（82.30mmol）, 66oHeating is stirred under C
Mix, condensing reflux 48h.
S2：Distilling apparatus, distilling off solvent tetrahydrofuran are changed to after the reaction was complete；Then DMF lysates are used, are stirred
12h.Filtering, obtains clear filtrate, after rotating half filtrate, finally with ethyl acetate reprecipitation product, then uses ethyl acetate
Washed product three times, vacuum drying 12 it is small when.
S3：0.8g TbCl are added in 100ml three-necked flasks3.6H2O and 40ml alcohol is as solvent, and ultrasonic vibration is extremely
TbCl3.6H2O is completely dissolved, by six（4- potassium formate phenoxyls）Ring tripolyphosphazene is dissolved in 20ml alcohol, is then added drop-wise to
In three-necked flask with TbCl3.6H2O reacts, reaction time 5h, reaction temperature 60oC。
S4：After the completion of reaction, the impurity such as grease are filtered out while hot, then rotate reaction dissolvent, then with anhydrous second
Alcohol washing reaction products several times, finally reprecipitation goes out product, prepared tripolyphosphazene crosslinking terbium coordination compound in ethyl acetate
As shown in formula I：
Formula I.
Prepared tripolyphosphazene is crosslinked terbium coordination compound in ultraviolet light（365nm）Pure green light hair is shown under excitation
Penetrate.In infrared spectrum（Fig. 1）1646cm-1The absworption peak at place is attributed to carbonyl and Tb in ligand3+Carbonyl after ion coordination is stretched
Contracting vibration peak, the appearance at the peak show ligand and Tb3+Success is coordinated.The excitation peak of the complex（Fig. 2）Be shown in 275nm~
There are a very wide bands of a spectrum between 400nm.Emission spectrum（Fig. 3）Show the characteristic emission bands of a spectrum of terbium ion, its green light characteristic
It is emitted as 545nm.
Embodiment 2：Tripolyphosphazene is crosslinked the preparation method of rare-earth complexes luminous material：
S1：Tetrahydrofuran 100ml hexa chloro cyclotripolyphosphazenes 2.50g is sequentially added in 250ml single-necked flasks
（7.19mmol）, P-hydroxybenzoic acid 7.13g（51.59mmol）, potassium carbonate 11.38（82.30mmol）, 66oHeating is stirred under C
Mix, condensing reflux 48h.
S2：Distilling apparatus, distilling off solvent tetrahydrofuran, then with DMF lysates, stirring are changed to after the reaction was complete
12h.Filtering, obtains clear filtrate, after rotating half filtrate, most with ethyl acetate reprecipitation product, then is washed with ethyl acetate
Product is washed three times, when vacuum drying 15 is small.
S3：0.8g EuCl are added in 100ml three-necked flasks3.6H2O, 40ml alcohol are as solvent, and ultrasonic vibration is extremely
EuCl3.6H2O is completely dissolved, by six（4- potassium formate phenoxyl ring tripolyphosphazenes are dissolved in 20ml alcohol, are then added drop-wise to
In three-necked flask with TbCl3.6H2O reacts, reaction time 5h, reaction temperature 60oC。
S4：After the completion of reaction, the impurity such as grease are filtered out while hot, then rotate reaction dissolvent, then with anhydrous second
Alcohol washing reaction products several times, finally reprecipitation goes out product, prepared tripolyphosphazene crosslinking europium complex in ethyl acetate
As shown in formula II：
Formula II.
As shown in Figure 1, prepared tripolyphosphazene is crosslinked europium complex in ultraviolet light（365nm）Shown under excitation pure
Red emission.In infrared spectrum（Fig. 4）1654cm-1The absworption peak at place is attributed to carbonyl and Eu in ligand3+After ion coordination
Carbonylic stretching vibration peak, the appearance at the peak shows ligand and Eu3+Success is coordinated.The emission spectrum of tripolyphosphazene europium complex
（Fig. 5）The characteristic emission bands of a spectrum of europium ion are shown, its feature red emission is 625nm.
Embodiment 3- 5 uses the method identical with Examples 1 and 2, the difference is that the proportioning of parameter, specific such as table 1：
Table 1
The structural formula for the product that embodiment 3- 5 is obtained is identical with example 1.
Finally illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to compared with
The present invention is described in detail in good embodiment, it will be understood by those of ordinary skill in the art that, can be to the skill of the present invention
Art scheme technical scheme is modified or replaced equivalently, without departing from the objective and scope of technical solution of the present invention, it should all cover at this
Among the right of invention.
Claims (1)
1. tripolyphosphazene is crosslinked the preparation method of rare-earth terbium complex luminescent material, it is characterised in that：Include the following steps：
S1：Six（4- potassium formate phenoxyls）The preparation of ring tripolyphosphazene：It is 1 in molar ratio:1~10:5 ~ 20 ratio takes chlordene
Ring tripolyphosphazene, P-hydroxybenzoic acid and potassium carbonate mixing, add in good solvent and stir, dissolve solid, by reaction temperature liter
Temperature is to 40~90 DEG C, when sustained response 36~48 is small；Wherein, the hexa chloro cyclotripolyphosphazene is NH4Cl and PCl5In chlorobenzene solution
In, and react and be made under the catalysis of composite catalyst zinc oxide/pyridine；The good solvent is dichloromethane, chloroform, four
One or more in hydrogen furans, N,N-dimethylformamide or dimethyl sulfoxide (DMSO)；
S2：Six（4- potassium formate phenoxyls）The purification of ring tripolyphosphazene：Step S1 products therefroms are cooled to room temperature, with distillation
Device distilling off solvent, then with DMF lysates, agitation and filtration, obtains clear filtrate, is finally produced with ethyl acetate reprecipitation
Thing, then with ethyl acetate washed product for several times, when vacuum drying 12~24 is small,Described six（4- potassium formate phenoxyls）Ring three Polyphosphazene can be coordinated with six rare earth ions at the same time；
S3：Tripolyphosphazene is crosslinked the preparation of rare-earth terbium complex：It is 1 in molar ratio:1 ~ 10 ratio takes TbCl3.6H2O and six
（4- potassium formate phenoxyls）Ring tripolyphosphazene, is then dissolved in respectivelyAlcoholIn fully dissolve, then by TbCl3.6H2O solution and
Six（4- potassium formate phenoxyls）Ring tripolyphosphazene solution mixes, and is reacted, and reaction temperature is 40~90 DEG C, response duration
Between be 4~8h；
S4：Tripolyphosphazene is crosslinked the purification of rare-earth terbium complex：After the completion of step S3 reactions, grease impurity is filtered out while hot,
Then the solvent in reaction is rotated, then with absolute ethyl alcohol washing reaction products several times, the last reprecipitation in ethyl acetate
Go out product.
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| CN106432341B (en) * | 2016-09-12 | 2018-05-15 | 重庆理工大学 | Hyperbranched tripolyphosphazene terpyridyl and preparation and the recognition methods to metal ion |
| CN109232654B (en) * | 2018-11-08 | 2020-07-28 | 重庆理工大学 | Eu/Tb-TCP-COOH complex luminescent material and preparation method and application thereof |
| CN110003278B (en) * | 2019-04-23 | 2021-07-27 | 重庆理工大学 | Visible light excited six-core triphosphazene europium complex luminescent material and preparation method and application thereof |
| CN110330664B (en) * | 2019-07-18 | 2021-08-03 | 重庆理工大学 | Eu/Tb-BHM-COOH complex and preparation method and application thereof |
| CN111560120A (en) * | 2020-06-19 | 2020-08-21 | 湖北科技学院 | Preparation method of two-dimensional magnetic coordination polymer based on cyclotriphosphazene derivative |
| CN112980431B (en) * | 2021-01-29 | 2022-10-21 | 上海工程技术大学 | Fluorescent material based on cyclotriphosphazene and preparation method and application thereof |
| CN113372529B (en) * | 2021-04-26 | 2022-10-28 | 北京化工大学 | Preparation method of polyphosphazene self-repairing elastomer |
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| US6221906B1 (en) * | 1999-03-26 | 2001-04-24 | Korea Institute Of Science And Technology | Platinum complex conjugated to cyclotriphosphazene, its preparation, and anticancer agent comprising the same |
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